Cr-doped diamond-like carbon (Cr-DLC) films with Cr contents ranging from 3 up to 20 at. % were synthesised in a codeposition process with HiPIMS (Cr deposition) and DC-pulsed technology (C deposition). The application of HiPIMS at low frequencies was observed to significantly enhance the energy density during the Cr plasma discharge due to the interaction of Cr–C species. The higher energy bombardment at low HiPIMS frequencies allowed doping with Cr the DLC structure avoiding the graphitization of the carbon structure. EELS spectroscopy was used to evaluate sp3 content and Raman was used for sp2 structural characterization of the films. Enhanced mechanical properties (hardness up to 30 GPa) were observed with nanoindentation for Cr-doped DLC at low frequencies. High temperature nanoindentation tests were also performed from room temperature to 425 °C in order to evaluate the evolution of hardness and Young Modulus with temperature. The results showed that the mechanical properties at high temperature mainly depend on the initial sp3-sp2 structure. Tribological tests were carried out in air from room temperature to 250 °C. Cr-doped DLC coatings deposited by low-frequency HiPIMS showed lower friction and wear compared to undoped DLC.